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Título: | Reversible Light-Induced Dimerization of Secondary Face Azobenzene-Functionalized β-Cyclodextrin Derivatives |
Autor: | Rivero-Barbarroja, Gonzalo; Fernández-Clavero, Carlos; García-Iriepa, Cristina; Marcelo, Gema CSIC ORCID; Padilla-Pérez, M Carmen; Neva, Tania; Benito, Juan M. CSIC ORCID CVN ; Maisonneuve, Stéphane; Ortiz Mellet, Carmen; Xie, Juan; García Fernández, José M; Mendicuti, Francisco | Palabras clave: | Reversible Light-Induced β-Cyclodextrin Dimerization Secondary Face Azobenzene |
Fecha de publicación: | 21-jun-2023 | Editor: | ACS Publications | Citación: | Journal of Organic Chemistry 88:8674–8689 (2023) | Resumen: | β-cyclodextrin (βCyD) derivatives equipped with aromatic appendages at the secondary face exhibit tailorable self-assembling capabilities. The aromatic modules can participate in inclusion phenomena and/or aromatic-aromatic interactions. Supramolecular species can thus form that, at their turn, can engage in further co-assembling with third components in a highly regulated manner; the design of nonviral gene delivery systems is an illustrative example. Endowing such systems with stimuli responsiveness while keeping diastereomeric purity and a low synthetic effort is a highly wanted advancement. Here, we show that an azobenzene moiety can be "clicked" to a single secondary O-2 position of βCyD affording 1,2,3-triazole-linked βCyD-azobenzene derivatives that undergo reversible light-controlled self-organization into dimers where the monomer components face their secondary rims. Their photoswitching and supramolecular properties have been thoroughly characterized by UV-vis absorption, induced circular dichroism, nuclear magnetic resonance, and computational techniques. As model processes, the formation of inclusion complexes between a water-soluble triazolylazobenzene derivative and βCyD as well as the assembly of native βCyD/βCyD-azobenzene derivative heterodimers have been investigated in parallel. The stability of the host-guest supramolecules has been challenged against the competitor guest adamantylamine and the decrease of the medium polarity using methanol-water mixtures. The collective data support that the E-configured βCyD-azobenzene derivatives, in aqueous solution, form dimers stabilized by the interplay of aromatic-aromatic and aromatic-βCyD cavity interactions after partial reciprocal inclusion. Photoswitching to the Z-isomer disrupts the dimers into monomeric species, offering opportunity for the spatiotemporal control of the organizational status by light. | Versión del editor: | https://pubs.acs.org/doi/epdf/10.1021/acs.joc.3c00564 | URI: | http://hdl.handle.net/10261/355056 | DOI: | 10.1021/acs.joc.3c00564 | ISSN: | 0022-3263 |
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